Effect of iron on reactivity of vanillin in wine models /

Phenolic compounds are important components of grapes and wines. They have been found to have important roles in grape and wine systems and properties that are beneficial for human health. Vanillin (3-methoxy-4-hydroxybenzaldehyde) is a phenolic compound coming from the oxidative degradation of lignin in oak-barrels during the aging of wine. Vanillin is an important flavour component of wine and its concentration in wine influences significantly the aroma and flavour of wine. The concentration of vanillin in wine is affected by various factors including the presence of metal ions. In this work, by using HPLC, HPLC-MS, and MS technologies, iron (III) cations were found to affect the oxidation of vanillin in a model system of wine, and the product of the oxidation was identified as divanillin. The mechanism of the redox reaction between vanillin and Fe^"^ is thought to follow that of other phenol oxidations. Increasing the concentration of Fe ^ in the model system accelerates divanillin production. The best pH condition for the divanillin production in the system is the range of 3.0 ~ 3.5. Increasing temperature from 20°C to 40°C accelerates the divanillin production. Divanillin was found to exist in three commercial red wines in this work. Keeping the storage temperature cool and decreasing the contact of grapes and wines with iron are two major measures suggested by this work in order to decrease the oxidation of vanillin during the making and aging of wine.

Role of family eating practices on daily nutrient intakes, dietary patterns and measures of body composition in peri-adolescents

Although family eating practices (FEPs) playa role in the formation of eating practices in children, there is a lack of evidence regarding the role of FEPs on obesity (DB) risk. The purpose of this thesis was to assess the role of child, mother 'and father eating practices (CEPs; MEPS; FaEPs) on nutrient intakes, dietary patterns and body composition. Data were collected on approximately 2,400 peri-adolescents (s250 with complete covariate data). Dietary patterns were assessed using scores that reflected how closely participants followed DASH and Health Canada (HC) recommendations. In girls, poor CEPs, MEPs and FaEPs were associated with increased BMI and risk of overweight and poor dietary patterns according to DASH, and DASH and HC, respectively. In boys, poor CEPs and FaEPs were associated with increased monounsaturated and trans fat, and Vitamin C intakes, respectively. These findings suggest FEPs are associated with DB risk, particularly in girls.

Half-sandwich silane complexes of ruthenium and iron : synthesis, structure and application to catalysis

The present thesis describes syntheses, structural studies, and catalytic reactivity of new non-classical silane complexes of ruthenium and iron. The ruthenium complexes CpRu(PPri3)CI(T]2-HSiR3) (1) (SiR3 = SiCh (a), SiClzMe (b), SiCIMe2 (c), SiH2Ph (d), SiMe2Ph (e» were prepared by reactions of the new unsaturated complex CpRu(PPri3)CI with silanes. According to NMR studies and X-ray analyses, the complexes la-c exhibit unusual simultaneous Si··· H and Si··· CI-Ru interactions. The complex CpRu(PPri3)CI was also used for the preparation of the first examples of late transition metal agostic silylamido complexes CpRu(PPri3)(N(T]2-HSiMe2)R) (2) (R= Ar or But), which were characterized by NMR spectroscopy. The iron complexes CpFe(PMePri2)H2(SiR3) (3) (SiR3 = SiCh (a), SiClzMe (b), SiCIMe2 (c), SiH2Ph (d), SiMe2Ph (e» were synthesized by the reaction of the new borohydride iron complex CpFe(PMePri2)(B~) with silanes in the presence NEt3. The complexes 3 exhibit unprecedented two simultaneous and equivalent Si··· H interactions, which was confirmed by X-ray analyses and DFT calculations. A series of cationic ruthenium complexes [CpRu(PR3)(CH3CN)(112-HSiR'3)]BAF (PR3 = PPri 3 (4), PPh3 (5); SiR'3 = SiCh (a), SiClzMe (b), SiClMe2 (c), SiH2Ph (d), SiMe2Ph (e» was obtained by substitution of one of the labile acetonitrile ligands in [CpRu(PR3)(CH3CNh]BAF with sHanes. Analogous complexes [TpRu(PR3)(CH3CN)(T]2 -HSiR' 3)]BAF (5) were obtained by the reaction of TpRu(PR3)(CH3CN)CI with LiBAF in the presence of silanes. The complexes 4-5 were characterized by NMR spectroscopy, and the observed coupling constants J(Si-H) allowed us to estimate the extent of Si-H bond activation in these compounds. The catalytic activity in hydrosilylation reactions of all of the above complexes was examined. The most promising results were achieved with the cationic ruthenium precatalyst [CpRu(PPri3)(CH3CN)2t (6). Complex 6 shows good to excellent catalytic activity in the hydrosilylation of carbonyls, dehydrogenative coupling of silanes with alcohols, amines, acids, and reduction of acid chlorides. We also discovered very selective reduction of nitriles and pyridines into the corresponding N-silyl imines and l,4-dihydropyridines, respectively, at room temperature with the possibility of catalyst recycling. These chemoselective catalytic methods have no analogues in the literature. The reactions were proposed to proceed via an ionic mechanism with intermediate formation of the silane a-complexes 4.

Dietary Intakes and Periodontal Outcomes After Sanative Therapy

Diet has an important role in the maintenance of oral health, but the relationship between diet and clinical outcomes following sanative therapy (ST) has not been investigated. Due to their antioxidant and anti-inflammatory properties, we hypothesized that periodontal patients with higher intakes of vitamin C, vitamin D, eicosapentaenoic acid (EPA) or docosahexaenoic acid (DHA) would have greater reductions in probing depth (PD) after ST. Patients completed the Block food frequency questionnaire, a supplement use questionnaire and had their serum 25-hydroxyvitamin D measured. There were no significant associations between intakes of vitamin C, vitamin D, EPA, DHA and PD. There were, however, negative associations between intakes of linoleic acid, α- linolenic acid or total vegetable intake and PD, as well as a positive association between the total omega-6/omega-3 ratio and PD (p < 0.05). Therefore, dietary intakes of essential fatty acids and vegetables may be important modulators of periodontal outcomes following ST.

Modeling short-range ballistic missile defense and Israel's Iron Dome system

This paper develops a model of short-range ballistic missile defense and uses it to study the performance of Israel’s Iron Dome system. The deterministic base model allows for inaccurate missiles, unsuccessful interceptions, and civil defense. Model enhancements consider the trade-offs in attacking the interception system, the difficulties faced by militants in assembling large salvos, and the effects of imperfect missile classification by the defender. A stochastic model is also developed. Analysis shows that system performance can be highly sensitive to the missile salvo size, and that systems with higher interception rates are more “fragile” when overloaded. The model is calibrated using publically available data about Iron Dome’s use during Operation Pillar of Defense in November 2012. If the systems performed as claimed, they saved Israel an estimated 1778 casualties and $80 million in property damage, and thereby made preemptive strikes on Gaza about 8 times less valuable to Israel. Gaza militants could have inflicted far more damage by grouping their rockets into large salvos, but this may have been difficult given Israel’s suppression efforts. Counter-battery fire by the militants is unlikely to be worthwhile unless they can obtain much more accurate missiles.

Iron Mountain Route Railway schedule: the great through line St. Louis, Arkansas and Texas to the Hot Springs of Arkansas

Iron Mountain Route Railway schedule: the great through line St. Louis, Arkansas and Texas to the Hot Springs of Arkansas.

Letter to S.D. Woodruff from William Colburn with the letterhead “Office of Detroit Bridge and Iron Works”

Letter to S.D. Woodruff from William Colburn with the letterhead “Office of Detroit Bridge and Iron Works” regarding stating that he closed up the business with Dewey’s. He states that “we” now have “warranty deeds” from them for exclusive rights for all time for hunting, shooting and trapping, Mar. 20, 1884.

Letter to S.D. Woodruff from A. Jeffrey importer of Hardware, Iron, Steel, and Window Glass of St. Catharines, Ont.

Letter to S.D. Woodruff from A. Jeffrey importer of Hardware, Iron, Steel, and Window Glass of St. Catharines, Ont. A. Jeffrey says that he will be able to supply Mr. Woodruff with glass and iron pipe, June 7, 1875.

Letter to S.D. Woodruff from A. Jeffrey importer of Hardware, Iron, Steel, and Window Glass of St. Catharines, Ont.

Letter to S.D. Woodruff from A. Jeffrey importer of Hardware, Iron, Steel, and Window Glass of St. Catharines, Ont. regarding breakage and freight, June 23, 1875.

Receipt from A. Jeffrey importer of Hardware, Iron, Steel, Nails and etc

Receipt from A. Jeffrey importer of Hardware, Iron, Steel, Nails and etc. regarding payment received on glass panes, Nov. 12, 1875.

Receipt from Gourlay Brothers for iron thimble and stopper

Receipt from Gourlay Brothers for iron thimble and stopper, Sept. 9, 1876.

Receipt from Watkins and Harris, Wholesale and Retail Ironmongers, Toronto, Ontario for iron

Receipt from Watkins and Harris, Wholesale and Retail Ironmongers, Toronto, Ontario for iron, May 11, 1838.